Sulfone-ester compounds

ABSTRACT

SULFONE-ESTER COMPOUNDS OF THE GENERAL FORMULA   (R&#39;&#39;-COO)N-AR&#39;&#39;-SO2-AR-OOC-R   WHERE N IS 0 OR 1, AR AND AR&#39;&#39; REPRESENT ARYL RADICALS, AND R AND R&#39;&#39; REPRESENT LONG CHAIN ALIPHATIC RADICALS.

United States Patent Oihce 3,654,323 Patented Apr. 4, 1972 ABSTRACT OF THE DISCLOSURE sulfone-ester compounds of the general formula (R-ii0)n-ArS0 ArOi3R where n is 0 or 1, Ar and Ar represent aryl radicals, and R and R represent long chain aliphatic radicals.

This invention relates to novel and useful long chain or higher molecular weight aliphatic monoand diesters of diaryl sulfones.

Certain sulfone-ester compounds are known in the art and have been disclosed in various patents and publications. For example, hydroxyalkyl esters of sulfonyl dibenzoic acid have been reported as useful in preparing resins, and compounds such as ethyl 4-(dodecylsulfonyl) butanoate are known as plasticizers in vinyl resins and sulfonyl bis aliphatic esters are known as plasticizers for thermoplastic resins. These and similar compounds are disclosed, for example, in US. Pat. Nos. 2,614,120; 2,692,207; 2,969,387; 3,028,416 and 3,194,830. Also there have heretofore been reported lower dialkyl esters of dihydroxydiphenyl sulfone such as the diacetate and dibutyrate esters, as mentioned in Chemical Abstracts, vols. 32, 5918; 37, 5040 and 52, 20,0136.

In accordance with the present invention there have been discovered novel diaryl sulfone monoand diester compounds having the general formula where n is 0 or 1, indicating a monoor diester, Ar and Ar represent the same or different aryl radicals and R and R represent the same or different long chain aliphatic radicals containing from about 7 to 100 carbon atoms. The said esters have useful properties not possessed by the lower aliphatic esters.

In the aforesaid general formula R and R are the same or different aliphatic radicals, straight or branched chain, as exemplified by alkyls such as n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, di-isobutylcarbinyl, decyl, undecyl, dodecyl, lauryl, myristyl, cetyl, stearyl and the like or an alkenyl hydrocarbon group exemplified by n-octenyl, diisobutenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and the like containing at least 7 carbon atoms as well as an aliphaticpolyene such as isopreneyl or squaleneyl. R and -R can also be aliphatic radicals containing even greater numbers of carbon atoms, up to about 100, said aliphatic hydrocarbon radicals being derived, for example, from oxidized paraflin Waxes, microcrystalline waxes and synthetic Fischer-Tropsch waxes, said oxidized waxes generally containing from 18 to 100 carbon atoms per molecule, and having saponification values of between about 15 and 160, acid values of from about to 60, and molecular weight of between about 280 and 1600, and, more particularly, oxidized microcrystalline and Fischer-Tropsch waxes containing from about 35 to 80 carbon atoms and being predominately paralfnic.

The aforesaid aliphatic hydrocarbon radicals can contain one or more functional group substituents. Exemplary are oxygen-containing radicals such as octoxyethyl, di-butyoxypropyl, dioctoxypropyl, di-octenoxypropyl and other alkoxy-substituted aliphatic groups; halosubstituted radicals such as chlorodecyl, chlorododecyl, bromooctyl and bromooctadecyl, as well as long chain alkenyl radicals containing one or more halogen substituents such as monoand polychlorodiisobutenyl. R or R can also represent an aliphatic group containing sulfur such as those having the formula onz-on-rormn or CH -CI-I S--(CH where n is an integer of at least 5, and other similar thioalkyl radicals.

Other functional group substituents which can be present in the aforesaid aliphatic hydrocarbon radicals are exemplified by amino and amido and their N-substituted derivatives; hydroxy and hydroxyalkyl radicals such as hydroxymethyl, hydroxyethyl and higher homologs, hydroxyamino, hydroxyimino and hydroxyphosphinyl; phosphorus substituents such as phospho, phosphono, phosphoranyl, phosphoro, phosphoroso, phosphino and phosphinothioyl; sulfur-containing functional groups such as sulfamino, sulfamyl, sulfanilamido, sulfarilyl, mercapto, sulfino, sulfinyl, sulfo, sulfonyl and the like; nitro, nitramino, nitrosamino, nitrosimino and nitroso; carbonyl, carboxy and carbonyldioxy; acyl radicals such as acetyl, acetoacetyl, butyryl, hexanoyl, lactoyl, lauroyl and dodecanoyl; and aromatic groups such as benzamido, benzenesulfonyl, benzimido, benzoyl, benzylthio, benzoyloxy, benzyloxy, etc.

Embodiments of the present invention of particular value are diaryl sulfone monoand diesters in which the aforesaid R and R groups are straight or branched chain alkyl or alkenyl radicals containing from 7 to 22 carbon atoms, especially monoand di-esters derived from long chain aliphatic monocarboxylic acids such as lauric, palmitic, stearic, oleic and linoleic, saturated tertiary monocarboxylic acids, and other aliphatic monocarboxylic acids containing particularly 918 carbon atoms.

The diaryl sulfone ester compounds of the present invention encompass not only diphenyl sulfone long chain aliphatic esters, which are the particularly preferred embodiments, but the S0 group can be linked to other aromatic radicals. Thus, in the aforesaid general formula, Ar and Ar can represent aryl radicals such as those derived from aromatic monocyclic hydrocarbons and aromatic polycyclic hydrocarbons exemplified by benzene, bibenzyl, biphenyl, cumene, cymene, ethyl benzene, fluorene, toluene, xylene, naphthalene, phenanthrene and styrene, as well as polyphenyl hydrocarbons such as stilbene and terphenyl. The sulfone can contain some or different aryl radicals. Exemplary asymmetrical diaryl sulfones, which can be reacted to form the novel sulfoneester compounds of the present invention, are disclosed, for example, in US. Pat. Nos. 2,998,453; 2,998,454; 3,125,604; 3,225,104 and 3,402,204.

The aryl radicals of the novel diaryl sulfone ester compounds of the present invention, as a general rule, contain nuclearly substituted groups replacing an aromatic hydrogen. Exemplary are monoand diesters derived from hydroxyaryl sulfones such as alkyl-substituted hydroxyaryl sulfones as disclosed in US. Pat. No. 3,383,- 421, methoxylated or hydroxybenzylated dihydroxy diphenyl sulfones as disclosed in US. Pat. Nos. 3,225,104 and 3,230,198; monoethers of 2,2 dihydroxydiphenyl sulfone as described in U.S. Pat. No. 3,408,422; or a compound such as 4-hydroxy 3 chlorophenyl sulfone, as disclosed in US. Pat. No. 2,314,379; or 5' chloro- 2,4-dihydroxydiphenyl sulfone and similar compounds as disclosed in U.S. Pat. No. 2,288,282.

Various methods for the preparation of the novel diaryl sulfone-ester compounds of the present invention can be 4- 1 The novel sulfone esters, and especially the diesters, of the present invention have been found to have a significant usefulness in the preparation of ashless greases by combining minor proportions, for instance, from about utilized so long as the essential 3 to of said esters with kerosene, mineral oil, 0 lubricating oil and other petroleum fractions. Stable lg grease compositions may be formed with no evidence TAITOT of insolubility or other instability, which is in marked linkage 1s tpbtamgd, lie. a1:3 oxygeg atiktlom ftirmlfirilig tlhe llnk contrast to heretofore known lower alkyl diesters which etween t 6 car y Car 011 an e y fa Ca G 1 are incompatible with said petroleum fractions.

erally, the esters can be prepared by reactions utilizing The invention is further illustrated by the following long chain carboxylic acids but they are also formed examples which are not to be considered as limitative of through the use of long chain acid anhydrides, acid chloits scope. All temperatures recited are in degrees centirides, amides, nitriles, unsaturated hydrocarbons, ethers, grade.

aldehydes and ketones, and by dehydration of long chain EXAMPLE 1 alcohols and by alcoholysis and acidolysis. EXemplary s 20.0 g. (0.1 mol) of laur1c acid was mixed in a 100 tiss es 121222 163222 522; tr ine s with w e of phatic acid anhydride or an acid chloride with a diaryl phenyl sulfone and a Small piece of magnesium was added. The mixture was heated at a temperature of Home contamm'g a nucliarly sllbstlmted f 200-230 for about minutes and the acetic acid a catalyst sud} as magnfasl'um 'bemg p m.the i formed was removed by vacuum distillation. The mixchlor1de react1on; reacting a long cham aliphatic amide ture was cooled to about 1500 and poured with Stirring 5 wlth hylhmiyphenyl Sulfone Wlth a halogenated into 200 ml. of methanol. The precipitate which formed 239 i i f l 3; was identified as the lauric acid diester of 4,4-dihydroxyg g O m n es W a c0 0 an diphenyl sulfone. The yield was 91.5% of theoretical; Preferably the novel sulfone-ester compounds are pre- EXAMPLE 2 A I pared by direct esterification between a hydroxy diaryl A mixture f 75 3 msl) of 4 4 sulfone, such as dihydroxydiphenyl sulfone, and a long phenyl lf 171 (Q6 mol) f stearic acid d cham al1phat1c carboxylic acid, m an approxlmately 2 30 42 of 001 was stirred and heated slowly in a 1 to 1 molar ratio diester Pffiparation) or a 1 to 1 liter flask to a temperature of 1309-137 and held at molar ratio (for monoester preparation) and most suitthis temperature f about 1 HCl w evolved ably in the presence of a condensing agent such as P001 over the course f the reaction and a condenser was A particularly su1table method of preparation has been employed to prevent loss f p0c1 h mixture was found to be a transesterification reaction whereby the dedecanted slowly into about 500 f methanol d 213 2 53;253:1532? s 5 artisans 3 3 a 12 18 am res er 0 e su one were recovere fatty acid, is reacted with the monoor diacetate, or XA LE other lower alkyl ester, of hydroxydiphenyl sulfone or E MP 3 dihydroxydiphenyl sulfone so as to form the novel esters Excellent ashless grease compositions were prepared described herein. by combining, by weight 95% of. kerosene and 5% The novel sulfone esters described herein have varied of the lauric acid diester bf 4,4'-dihydroxydiphenyl suluses, among which are starting materials for polyester fone or 5% of the palmitic acid diester of dihydroxydisulfone resinous compositions, as synthetic ester lubriphenyl sulfone. By contrast, when the diacetate of dicants, as intermediates, and for the preparation of ashless hydroxydiphenyl sulfone was combined with kerosene grease compositions by combining the esters with petroin various proportions, a stable grease could not be leum fractions. Liquid diesters of mixed fatty acids are formed since the diacetate was insoluble in the kerosene suitable as plasticizers for polyvinyl chloride resins. and no homogeneous blend could be obtained.

The following table lists melting point and elemental analysis data for a number of novel diesters made in EXAMPLE 4 accordance with the present invention. Said diesters Thi example ill t h preparation f a monowere prepared either by transesterification of the diacetate m 50 g, (0,2 mol) of 4,4-dihydroxydiphenyl sulfone or y reaction of long chain fatty acid d sulfone n was stirred with 43.7 g. (0.2 mol) of lauroyl chloride the presence of phosphorous oxychloride. In the table, at 16() 17() for approximately 2 hours. The mixture R refers to the at least 7 Carbon 910m Containing alkyl was then stirred into 300 ml. of methanol whereupon group 1n the general formula some crude lauric acid diester formed which was re moved by filtration. The filtrate was evaporated and 2 I: 9 the residual oil boiled with 150 ml. of ethylene dichlo- R c o 502 U ride, cooled and filtered to recover 17 g. of unreacted \J I 1\ 4,4-dihydroxy'diphenyl sulfone. The ethylene dichloride 3 2 2 3 filtrate was evaporated and the oily residue stirred with and all of the esters are those of 4,4'-'dihydroxydiphenyl ligroifl precipitate the crude Y Crystals of lamb sulfone. acid monoester of 4,4-dihydroXy d1phenyl sulfone. After TABLEI Elemental analysis Theoretical Determined Percent Percent Percent Percent; Percent Percent R M.P., 0 H s I o H s CH6(CH2)6 51-53 67.0 7.5 6.3 66.97 7.73 6.49 011303151238-.- -67 68.8 8.25 5.73 67.98 8.25 5 84 OH3(CH2)io 75.5-77.5 70.36 8.80 5.21 70.22 8.97 5 53 CH3(CH2)lZ---.- 84-85 71.50 9.30 4.77 71.76 9.35 5.11 oHi(oHa)1i-. 87-88 72.5 9.73 4.40 72.37 10.00, 4.62 CH3(CH2)16-- 91-92 73.64 10.0 4.08 73.29 10.2 4.26 CH5(CH2)20...-. 89-94 75.2 10.5 3.58 75.48 10.44 3.92

recrystallization from methanol, 21 g. (24% yield based on 4,4-dihydroxy diphenyl sulfone) of the pure monoester were recovered, melting at 70-71. The elemental analysis of the monoester (C H O S) was as follows: Theoretical (percent): C, 66.70; H, 7.40; S, 7.40. Determined (percent): C, 66.81; H, 7.47; S, 7.67.

EXAMPLE 5 A mixture of long chain diesters was prepared from 108.3 g. (0.6 mol) of a mixture of C C and C saturated tertiary monocarboxylic acids (sold under the designation Versatic Acid) and 100.2 g. of mixed isomers (4,4 and 2,4) of diacetoxy diphenyl sulfone according to the transesterification procedure described in Example 1. The crude yield of diester, an oil, was 164 g. (95% of theory). This crude liquid was dissolved in ether, extracted with aqueous sodium bicarbonate and the ether was volatilized to give a clear amber oil having a saponification number of 386 mg. of KOH/g. and an acid number of 7.8 mg. of KOH/g.

EXAMPLE 6 A solution of 10 parts by weight of polyvinyl chloride in 100 parts by weight of tetrahydrofuran was prepared and to this was added 3.5 parts by weight of the liquid diester prepared in Example 5 and a clear, stable solution was formed which, upon drying, gave a clear, smooth film. The film showed good flexibility and compatibility characteristics, said diester functioning effectively as a plasticizer for said PVC resin. A comparative test of the volatility of this diester plasticizer was performed by heating the film for 15 minutes at 150 as well as with a film prepared with dioctyl phthalate plasticized polyvinyl chloride. A weight loss of 0.8% was obtained with the film containing the diester of Example 5 compared with a weight loss of 1.1% for the PVC film plasticized with dioctyl phthalate.

What is claimed is:

1. A diaryl sulfone-ester having the general formula 0 o (R( JO),,ArSO ArO- 3R wherein n is 0 or 1, Ar and A1" represent aryl radicals, and R and R represent long chain aliphatic radicals containing from about 7 to carbon atoms.

2. An ester according to claim 1 wherein Ar and Ar represent phenyl.

3. An ester according to claim 1 wherein R and R represent alkyl or alkenyl radicals containing from 7 to 22 carbon atoms.

4. An ester according to claim 1 wherein n is 1, Ar and Ar are phenyl, and R and R are the alkyl portions of an aliphatic monocarboxylic acid containing from about 9 to 18 carbon atoms.

5. An ester according to claim 4 wherein the monocarboxylic acid is a fatty acid selected from the group consisting of lauric, palmitic, stearic, oleic and linoleic acids.

6. An ester according to claim 1 wherein n is 1, Ar and Ar are phenyl, and R and R are the alkyl portions of a mixture of C C and C saturated tertiary monocarboxylic acids.

References Cited UNITED STATES PATENTS 2,282,557 5/1942 Bruson 260-400 ELBERT L. ROBERTS, Primary Examiner U.S. Cl. X.R. 25248.2; 260-308 

